Ring-opening polymerization of cyclic siloxanes

Abstract

A process for producing high molecular weight silicones via ring-opening polymerization of cyclic siloxanes in the presence of a Lewis acid catalyst is described.

Description

Cross - Reference to Related Applications

[0001] This application claims the benefit of Patent Application Serial No. 18 / 519,796, filed on November 27, 2023, and also claims the benefit of Provisional Application Serial No. 63 / 385,127, filed on November 28, 2022, the entire contents of which are incorporated herein by reference. Field of the Invention

[0002] The present invention generally relates to a method for producing high - molecular - weight organosilicons via ring - opening polymerization of cyclic siloxanes in the presence of a Lewis acid catalyst. Background of the Invention

[0003] High - molecular - weight polysiloxanes (also known as silicone gums) with viscosities exceeding 20 million centipoise (cP) are found useful in a variety of applications, including, for example, anti - slip additives and anti - wear additives in coatings, such as leather polishes and coatings, and ply lubricants used in tire manufacturing.

[0004] The production of these high - molecular - weight organosilicon polymers requires significant facility and capital investment to produce silicone polymers on a production scale. These issues pose difficulties for smaller producers in manufacturing such organosilicon polymers.

[0005] The production of these high - molecular - weight polysiloxanes is typically accomplished via condensation reactions between lower - molecular - weight siloxanes. However, in such a process, insoluble small molecules such as, for example but not limited to, water, methanol, ethanol, propanol, butanol, and acetic acid are produced. This results in poor purity of the high - molecular - weight siloxanes as the insoluble by - products are considered impurities. To obtain a visually clear and pure product, the insoluble impurities must be removed, which increases the cost of the desired product.

[0006] High - molecular - weight polysiloxanes are typically produced using strong protonic acids or bases.

[0007] High - molecular - weight siloxanes are typically produced by condensation or ring - opening polymerization with limited control over chain - end functionality. Typical homofunctional polymers include hydroxyl, trimethylsilyl, hydride, and vinyl as chain - end groups. The ability to prepare heterotelechelic siloxane polymers is currently limited to anionic ring - opening polymerization. This method is restricted as it requires strict processes and preparations, more expensive raw materials, and the use of strong organolithium compounds which are usually hazardous.

[0008] Accordingly, there is a need to overcome one or more of the current drawbacks noted above. Brief Description of the Invention

[0009] Embodiments of the present invention surprisingly provide an effective and direct method for polymerizing one or more cyclic siloxanes. One or more cyclic siloxanes are combined with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture. One or more cyclic siloxanes have the formula

[0010]

[0011] wherein n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide.

[0012] In one embodiment, the product obtained from the reaction mixture has the formula (II) [(HO)R2SiO 1 / 2 2(R2SiO2 / 2) m , where m > n, a high molecular weight polysiloxane.

[0013] In another embodiment, the product obtained from the reaction mixture has the formula (III) [(HO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)], where m > n, a high molecular weight functionalized polysiloxane. Z can be, for example, a nucleophilic group such as an amine, an alkoxy group, a trialkylsiloxy group, an acetate, an alkyl ester, a silazanyl group, an aminosilyl group, an aminoorganosilicon group. Other suitable Z groups include, for example, water, cyanide, thiol, alcohol, a proton base (NaOH, KOH), an amine, an amide, an aminosilane, a halide, an azide, a phosphine compound, an inorganic hydride (NaH, LiAlH4), n-butyllithium and / or an organolithium reagent.

[0014] In another embodiment, the product obtained from the reaction mixture has the formula (IV) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(OH)], where m > n, a high molecular weight functionalized polysiloxane. T is an electrophilic functional group.

[0015] In yet another embodiment, the product obtained from the reaction mixture has the formula (V) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)], where m > n, a high molecular weight functionalized polysiloxane, wherein Z and T are as described herein.

[0016] This method provides advantages compared to currently known processes and high molecular weight polysiloxanes containing functionalized products. This method provides high molecular weight polysiloxanes, including functionalized products, using standard process equipment such as standard drum mixers and drum heaters without significant capital investment.

[0017] Suitable Lewis acids include trifluoromethanesulfonates(III), gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalides, organoboranes, and mixtures thereof.

[0018] One advantage of this embodiment is that no pressure is required to drive the reaction.

[0019] Another advantage of this embodiment is that the reaction can occur at ambient temperature or at a temperature less than about 60 °C.

[0020] Still further advantages of some embodiments are that no insoluble small molecules, such as potential by-products like water, short-chain alcohols (methanol, ethanol, propanol, butanol), and / or acetic acid, are formed.

[0021] Yet another advantage of the current embodiment is that no solvent is required during the reaction. Solvent is an option, but not necessary. Another advantage is that no protic acid is required in combination with the preferred Lewis acid bismuth trifluoromethanesulfonate.

[0022] Another advantage is that the molecular weight is controlled by equilibration reaction conditions including end groups such as hexamethyldisiloxane. For example, instead of adding a cyclic polysiloxane together with a catalyst and allowing the reaction to proceed, another component that caps the polymer is added. This capping effectively limits the growth of the polymer, and the final polymer molecular weight is adjusted by regulating the concentration of the capping in the system. For example, Example 15-32-1 (below) is a standard ROP and achieved an M of 612,172 g / mol in 166.8 hours w , while allowing the equilibration experiment (15-33-1) to react for 604.6 hours under the same conditions and only reaching an M of 66,465 g / mol wThe capping reagents include, but are not limited to, hexamethyldisiloxane, hexamethyldisilazane, short-chain PDMS, alkoxysilanes, alcohols, Grignard reagents, carboxylates, thiols, amines, amides, water, inorganic hydrides (NaH, LiAlH4), tetramethyldisiloxane, tetramethyldisilazane, tetramethyldivinyldisiloxane, tetramethyldivinyldisilazane, alkoxysilanes, aminosilanes, glycidylsilanes, and / or halosilanes, and nucleophiles that can generally act as capping agents.

[0023] Another advantage is the formation of asymmetric silanolates without the need for halosilane starting materials (such as chlorosilanes). These silanolates are made from the resulting polymers from the reaction of cyclic organosilicon and bismuth trifluoromethanesulfonate. The silanolates can be made with controllable molecular weight and functionality.

[0024] Another advantage can be that the preferred catalyst (bismuth trifluoromethanesulfonate) is significantly easier to handle and less hazardous than the published alternative Lewis acid examples (such as SbCl5 or tetrakis(pentafluorophenyl)borate).

[0025] Yet another advantage of the embodiments disclosed herein is the ability to synthesize the polysiloxanes described herein (including functionalized products) without the need for a large amount of equipment (such as twin-screw extruders) required for making gums. Advantageously, the components can be combined, for example, in a 55-gallon drum, mixed at ~65 °C for one day, and then placed in a hot room at ~70 °C for one week until the reaction is complete. This is also an additional benefit for energy efficiency and "greener" chemistry, which requires less effort, energy, and cost to achieve similar products.

[0026] Yet another advantage is that the method / process provides the ability to perform asymmetric or symmetric end-functionalization. This provides extended industrial significance because high molecular weight siloxanes are typically synthesized symmetrically, with the option of further functionalizing the end positions. Such processes result in increased product costs and also do not provide the ability to prepare asymmetric end-substituted products.

[0027] Although multiple embodiments have been disclosed, other embodiments of the invention will become apparent to those skilled in the art from the following detailed description. It is apparent that the invention is capable of modification in various obvious respects, all of which do not depart from the spirit and scope of the invention. Accordingly, the detailed description is to be regarded in an illustrative rather than a restrictive sense. Detailed Description

[0028] In the specification and claims, the terms "comprising," "including," and "containing" are open-ended terms and should be interpreted as "including but not limited to...". These terms encompass the more restrictive terms "consisting essentially of..." and "consisting of".

[0029] It should be noted that, as used in this specification and the appended claims, the singular forms "a", "an", "the", and "said" include plural referents unless the context clearly dictates otherwise. Similarly, the terms "a", "an", "one or more", "at least one", and "at least a kind" are used interchangeably herein. It should also be noted that the terms "comprising", "including", "containing", "characterized by", and "having" are used interchangeably.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications and patents specifically mentioned herein are incorporated by reference in their entirety for all purposes, including the description and disclosure of chemicals, instruments, statistical analyses, and methods reported in the publications that may be relevant to this invention. All references cited in this specification should be regarded as indicating the level of skill in the art. Nothing in this application shall be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention.

[0031] Suitable cyclic siloxanes for polymerization described herein include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), and hexadecamethylcyclooctasiloxane (D8) and mixtures thereof. In certain aspects, D4 and / or D5 are suitable cyclic siloxanes.

[0032] The present invention surprisingly provides an effective and direct method for polymerizing one or more cyclic siloxanes. One or more cyclic siloxanes are combined with a Lewis acid catalyst at a temperature of about 20 °C to about 400 °C to form a reaction mixture. One or more cyclic siloxanes have the formula

[0033]

[0034] wherein n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide.

[0035] In one embodiment, the product obtained from the reaction mixture has the formula (II) [(HO)R2SiO 1 / 2 2(R2SiO2 / 2) m , where m > n, a high molecular weight polysiloxane.

[0036] The reaction temperature can range from about ambient conditions (about 25 °C) to about 400 °C, but the process conditions are typically carried out below 100 °C. The reaction mixture can be heated to about 25 °C to about 100 °C, or about 25 °C to about 90 °C, or about 25 °C to about 80 °C, about 25 °C to about 70 °C, about 25 °C to about 60 °C, about 25 °C to about 50 °C, about 25 °C to about 40 °C, or about 25 °C to about 30 °C, and all temperatures and ranges including about 25 °C to about 100 °C (such as about 30 °C to about 100 °C, about 31 °C to about 100 °C, about 32 °C to about 100 °C, etc.), including about 40 °C to about 100 °C, about 50 °C to about 100 °C, etc., where all temperatures and ranges include about 30 °C to about 100 °C.

[0037] In another embodiment, the product obtained from the reaction mixture has the formula (III) [(HO)R2SiO 1 / 2 2(R2SiO2 / 2) m [SiO 1 / 2 R2(Z)], where m > n, a high molecular weight functionalized polysiloxane. Z can be, for example, an amine, an alkoxy group, a trialkylsiloxy group, an acetate, an alkyl ester, a silylazide group, a silylamino group, an aminoorganosilicon group.

[0038] In the context of this specification, unless otherwise specified, alkyl, alkenyl or alkynyl substituents or the alkyl, alkenyl or alkynyl moieties in substituents can be straight-chain or branched-chain. Examples of C1-C6 alkyl groups / parts include methyl, ethyl, propyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl. Examples of C2-C6 alkenyl groups / parts include vinyl, propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, 1,3-butadienyl, 1,3-pentadienyl, 1,4-pentadienyl and 1-hexadienyl. Examples of C2-C6 alkynyl groups / parts include ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl and 1-hexynyl.

[0039] Branched or unbranched alkyl, alkenyl or alkynyl groups can be substituted with one or more substituents such as halogens (Cl, I, Br), alkoxides, amino groups, thiolates, hydroxyl groups, etc.

[0040] Aryl groups include aromatic monocyclic or polycyclic groups having from 5 to 19 carbon atoms. Suitable examples include, but are not limited to, phenyl, naphthyl, pyridyl, furyl, imidazolyl, benzimidazolyl, thienyl, quinolinyl, indolyl, thiazolyl, and the like.

[0041] Amino groups include those having the formula –NR1R2, where R1 and R2 are each independently an alkyl, alkenyl, or alkynyl group, which may be further substituted with substituents such as those indicated above.

[0042] Alcoholate groups include those having the formula -OR1, where R1, as described above, is an alkyl group, an alkenyl group, which may be further substituted with substituents such as those indicated above.

[0043] In another embodiment, the product obtained from the reaction mixture has the formula (IV) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(OH)], where m > n, a high molecular weight functionalized polysiloxane. T is an electrophilic functional group such as a hydrogen atom, acrylate, methacrylate, isocyanate, isothiocyanate, epoxide, alkyl halide, α-β unsaturated olefin, alkyne, nitrile, aldehyde, ketone, alkoxysilane, glycidylsilane, aminosilane, halosilane, phosphine compounds, borane, haloborane, sodium hydride, n-butyllithium, organolithium reagents, methyl methacrylate, methyl acrylate, and / or butyl acrylate.

[0044] In still another embodiment, the product obtained from the reaction mixture has the formula (V) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)], where m > n, a high molecular weight functionalized polysiloxane, where Z and T are as described herein.

[0045] One of ordinary skill in the art will appreciate that the reactions described herein provide an opportunity to functionalize reaction intermediates with one or more capping / functionalizing reagents. Those listed herein are suitable for such capping / functionalizing, but are not limited to those provided.

[0046] Lewis acids are known in the art and have their fundamental properties, which are compounds or ionic substances that can accept an electron pair from a donor compound such as a Lewis base. Lewis acids include, for example, H + 、K + 、Mg 2+ 、Fe 3+ 、BF3、CO2、SO3、RMgX、AlCl3、Br2. Lewis bases include, for example, OH- 、 F - 、 H2O, ROH, NH3, SO4 2- 、 H - 、 CO, PR3 and C6H6.

[0047] The Lewis acids also include trifluoromethanesulfonates (III), gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalides, organoboranes, and mixtures thereof.

[0048] The concentration of the Lewis acid in the reaction mixture should be from about 10 ppm to about 5000 ppm based on the weight of the cyclic siloxane. Suitable ranges include from about 50 ppm to about 4500 ppm, from about 100 ppm to about 3000 ppm, from about 200 ppm to about 2000 ppm, from about 300 ppm to about 1000 ppm, from about 400 ppm to about 500 ppm, and all values and ranges from about 10 ppm to about 5000 ppm based on the weight of the cyclic siloxane. This includes values and ranges such as from about 11 ppm to about 4999 ppm, from about 12 ppm to about 4998 ppm, from about 13 ppm to about 4997 ppm, from about 14 ppm to about 4996 ppm, etc., which include 10 ppm, 20 ppm, 30 ppm up to 5000 ppm (in 10 ppm increments), including all ranges and sub-ranges therebetween.

[0049] The reaction mixture may include a chelating ligand. In one embodiment, the chelating ligand is a bis-imine, such as 1,2-bis-(2-di-isopropylphenyl)imino)ethane or 1,2-bis(2-di-tert-butylphenyl)imino)ethane, which is commercially available. Other chelating ligands are known and can be found in U.S. Patent No. 11,028,230 to Belowich et al., issued June 8, 2021, the content of which is incorporated herein by reference for all purposes.

[0050] The reaction may also include an optional solvent. However, a solvent is generally not necessary, which is an advantage of the current embodiment. If a solvent is utilized, it is an aprotic solvent such as tetrahydrofuran, toluene, dichloromethane, and / or trimethylsiloxy-capped polydimethylsiloxane.

[0051] In one embodiment, the cyclic siloxane and the Lewis acid catalyst can be combined at ambient temperature and allowed to polymerize. In other embodiments, the cyclic siloxane and the Lewis acid catalyst are combined and heated, typically to about 60 °C, until polymerization is complete and the remaining cyclic siloxane is not detected or is at an acceptable level (less than 2% by weight), as determined by suitable methods known in the art (such as by gas chromatography or by measuring the non-volatile content (NVC)).

[0052] An advantage of this embodiment is that no pressure is required to drive the reaction.

[0053] The polysiloxanes (including functionalized products) produced in this embodiment have a viscosity of from about 2,000 cP to about 200 million cP. For polysiloxanes, suitable ranges include from about 2,500 cP to about 190 million cP, from about 3,000 cP to about 180 million cP, from about 4,000 cP to about 170 million cP, from about 5,000 cP to about 160 million cP, from about 6,000 cP to about 150 million cP, and all values and ranges from about 2,000 cP to about 200 million cP. This includes values and ranges such as from about 2,100 cP to about 199 million cP, from about 2,200 cP to about 198 million cP, from about 2,300 cP to about 197 million cP, from about 2,400 cP to about 196 million cP, etc.

[0054] For polysiloxanes (including functionalized products) having a viscosity below 500,000 cP, at 25 °C, a Brookfield DV2T viscometer is used, with the LV spindle 3 or 4 at 30 rpm to 0.2 rpm. For polysiloxanes (including functionalized products) having a viscosity above 500,000 cP, at 25 °C, a Waters / TA instrument HR-3 rheometer is used, with a variable shear rate, for example, 0.01–1 / s shear.

[0055] The M of the polymers (II), (III), (IV) and / or (V) described herein wThe range can be from about 25,000 g / mol to about 1,000,000 g / mol. Suitable ranges include from about 30,000 g / mol to about 900,000 g / mol, from about 40,000 g / mol to about 750,000 g / mol, from about 100,000 g / mol to about 500,000 g / mol, from about 300,000 g / mol to about 700,000 g / mol, from about 400,000 to about 500,000 g / mol, and all values and ranges from about 25,000 g / mol to about 1,000,000 g / mol. This includes values and ranges such as from about 25,001 to about 999,999 g / mol, from about 25,002 g / mol to about 999,998 g / mol, from about 25,0003 g / mol to about 999,997 g / mol, from about 25,004 g / mol to about 999,996 g / mol, etc., including 25,010 g / mol, 25,020 g / mol, 25,030 g / mol up to 1,000,000 g / mol (in 10 g / mol increments), including all ranges and sub-ranges therebetween.

[0056] The M of the polymers (II), (III), (IV) and / or (V) described herein n The range can be from about 15,000 g / mol to about 600,000 g / mol. Suitable ranges include from about 30,000 g / mol to about 500,000 g / mol, from about 50,000 g / mol to about 450,000 g / mol, from about 100,000 g / mol to about 500,000 g / mol, from about 200,000 g / mol to about 400,000 g / mol, from about 300,000 to about 400,000 g / mol, and all values and ranges from about 15,000 g / mol to about 600,000 g / mol. This includes values and ranges such as from about 15,001 to about 599,999 g / mol, from about 15,002 g / mol to about 599,998 g / mol, from about 15,0003 g / mol to about 959,997 g / mol, from about 15,004 g / mol to about 599,996 g / mol, etc., including 15,010 g / mol, 15,020 g / mol, 15,030 g / mol up to 600,000 g / mol (in 10 g / mol increments), including all ranges and sub-ranges therebetween.

[0057] The polydispersity D of the polymers (II), (III), (IV) and / or (V) described herein can range from 1 to 2.5 and all values therebetween, including increments of 0.01 up to 2.5 (including all ranges and subranges therebetween), such as 1.01, 1.02, 1.03, 1.04, etc., in increments of 0.1 up to about 2.5.

[0058] In addition, the silicone polymers can be crosslinked to form a cured rubber which can be transparent. The silicone polymers ((II), (III), (IV), (V) alone or in combination) can be treated with a suitable crosslinking agent at ambient temperature or elevated temperature as described herein. The crosslinking agent can include 2 or 3 or more reactive groups per molecule that can combine with reactive groups. Suitable crosslinking agents include, for example but not limited to, tetraethyl orthosilicate, methyltrimethoxysilane, alkoxysilanes such as methyltrimethoxysilane, tetraethyl orthosilicate, methyltriethoxysilane, ethyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, n-octyltriethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilane, triethoxysilane, alcohols such as glycerol, trimethylolpropane, carboxylates such as ethylenediaminetetraacetic acid, citric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, agaricic acid, benzene-1,3,5-tricarboxylic acid, amines such as diethylenetriamine, benzene-1,3,5-triamine, triethylenetetramine, thiols such as pentaerythritol tetra(3-mercaptopropionate), propane trithiol, ethane-1,2-tetrathiol, azides such as boron triazide, tetrazidomethane, silicon tetrazide, amides, alkyl esters such as triglycerides, phosphine compounds, pentaerythritol, glycerol, sugar alcohols, polymeric polyols and / or Grignard reagents and those known in the art.

[0059] The following paragraphs numbered consecutively from 1 to 91 provide various aspects of the present invention. In one embodiment, in the first paragraph (1), the present invention provides 1. A method for polymerizing one or more cyclic siloxanes, the method comprising:

[0060] Combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula

[0061] wherein n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide; and

[0062] Obtaining a product from a mixture, wherein the product comprises formula (II) [(HO)R2SiO 1 / 2 2(R2SiO2 / 2) m , where m > n.

[0063] 2. The method according to paragraph 1, wherein n is from 2 to 10.

[0064] 3. The method according to paragraph 2, wherein n is from 3 to 8.

[0065] 4. The method according to paragraph 3, wherein n is from 4 to 8.

[0066] 5. The method according to any one of paragraphs 1 to 4, wherein the product has a viscosity of 2,000 cP to about 200 million cP.

[0067] 6. The method according to paragraph 5, wherein the product viscosity is about 2,500 cP to about 100 million cP.

[0068] 7. The method according to any one of paragraphs 1 to 6, wherein each R is a methyl or ethyl group.

[0069] 8. The method according to any one of paragraphs 1 to 6, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

[0070] 9. The method according to any one of paragraphs 1 to 8, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane and mixtures thereof.

[0071] 10. The method according to paragraph 9, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

[0072] 11. The method according to any one of paragraphs 1 to 10, wherein the Lewis acid catalyst is present in an amount of 10 ppm to 5,000 ppm based on the weight of the cyclic siloxane.

[0073] 12. The method according to any one of paragraphs 1 to 11, further comprising a solvent.

[0074] 13. The method according to paragraph 12, wherein the solvent is water.

[0075] 14. A method according to any one of paragraphs 1 to 13, wherein the reaction temperature is from about 40 °C to about 100 °C.

[0076] 15. A method according to paragraph 14, wherein the reaction temperature is from about 60 °C to about 70 °C.

[0077] 16. A method according to any one of paragraphs 1 to 15, further comprising a chelating ligand.

[0078] 17. A method according to paragraph 16, wherein the chelating ligand is a bisimine.

[0079] 18. A method according to any one of paragraphs 1 to 17, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

[0080] 19. A method according to any one of paragraphs 1 to 17, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

[0081] 20. A method according to any one of paragraphs 1 to 19, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

[0082] 21. A method according to any one of paragraphs 1 to 20, wherein the reaction mixture is stirred.

[0083] 22. A method according to any one of paragraphs 1 to 21, further comprising quenching the reaction mixture with a quenching agent.

[0084] 23. A method according to paragraph 22, wherein the quenching agent is an amine or water.

[0085] 24. A method for polymerizing one or more cyclic siloxanes, the method comprising:

[0086] Combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane comprises the formula

[0087] wherein n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide;

[0088] Treating the reaction mixture with a nucleophile Z; and

[0089] Obtaining a product from the mixture, wherein the product comprises the formula (III) [(HO)R2SiO 1 / 2(R2SiO2 / 2) m [SiO 1 / 2 R2(Z)] where m > n and Z includes amine, alkoxy group, trialkylsiloxy group, acetate, alkyl ester, silylazide, aminomethylsilyl group or aminoorganosilicon group.

[0090] 25. The method according to paragraph 24, wherein n is from 2 to 10.

[0091] 26. The method according to paragraph 25, wherein n is from 3 to 8.

[0092] 27. The method according to paragraph 26, wherein n is from 4 to 8.

[0093] 28. The method according to any one of paragraphs 24 to 27, wherein the product has a viscosity of 2,000 cP to about 200 million cP.

[0094] 29. The method according to paragraph 28, wherein the product viscosity is about 2,500 cP to about 100 million cP.

[0095] 30. The method according to any one of paragraphs 24 to 29, wherein each R is a methyl or ethyl group.

[0096] 31. The method according to any one of paragraphs 24 to 39, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

[0097] 32. The method according to any one of paragraphs 24 to 31, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane and mixtures thereof.

[0098] 33. The method according to paragraph 32, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

[0099] 34. The method according to any one of paragraphs 24 to 33, wherein the Lewis acid catalyst is present in an amount of 10 ppm to 5,000 ppm based on the weight of the cyclic siloxane.

[0100] 35. The method according to any one of paragraphs 24 to 34, further comprising a solvent.

[0101] 36. The method according to paragraph 35, wherein the solvent is water.

[0102] 37. The method according to any one of paragraphs 24 to 36, wherein the reaction temperature is from about 40 °C to about 100 °C.

[0103] 38. The method according to paragraph 37, wherein the reaction temperature is from about 60 °C to about 70 °C.

[0104] 39. The method according to any one of paragraphs 24 to 38, further comprising a chelating ligand.

[0105] 40. The method according to paragraph 39, wherein the chelating ligand is a bisimine.

[0106] 41. The method according to any one of paragraphs 24 to 40, wherein the chelating ligand is combined with the Lewis acid catalyst before the Lewis acid is combined with the cyclic siloxane.

[0107] 42. The method according to any one of paragraphs 24 to 40, wherein the chelating ligand is combined with the reaction mixture after the Lewis acid catalyst is combined with the cyclic siloxane.

[0108] 43. The method according to any one of paragraphs 24 to 42, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

[0109] 44. The method according to any one of paragraphs 24 to 43, wherein the reaction mixture is stirred.

[0110] 45. The method according to any one of paragraphs 24 to 44, further comprising quenching the reaction mixture with a quenching agent.

[0111] 46. The method according to paragraph 45, wherein the quenching agent is an amine.

[0112] 47. A method for polymerizing one or more cyclic siloxanes, the method comprising:

[0113] combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula

[0114] wherein n is from 1 to 20 and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide;

[0115] treating the reaction mixture with an electrophile T; and

[0116] A product is obtained from a mixture, wherein the product comprises formula (IV) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(OH)], where m > n, and T comprises an electrophile.

[0117] 48. The method according to paragraph 47, wherein n is from 2 to 10.

[0118] 49. The method according to paragraph 48, wherein n is from 3 to 8.

[0119] 50. The method according to paragraph 49, wherein n is from 4 to 8.

[0120] 51. The method according to any one of paragraphs 47 to 50, wherein the product has a viscosity of 2,000 cP to about 200 million cP.

[0121] 52. The method according to paragraph 51, wherein the product viscosity is about 2,500 cP to about 100 million cP.

[0122] 53. The method according to any one of paragraphs 47 to 52, wherein each R is a methyl or ethyl group.

[0123] 54. The method according to any one of paragraphs 47 to 52, wherein each R is independently one of a methyl group, an ethyl group, or a phenyl group.

[0124] 55. The method according to any one of paragraphs 47 to 54, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane, and mixtures thereof.

[0125] 56. The method according to paragraph 55, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

[0126] 57. The method according to any one of paragraphs 47 to 56, wherein the Lewis acid catalyst is present in an amount of 10 ppm to 5,000 ppm based on the weight of the cyclic siloxane.

[0127] 58. The method according to any one of paragraphs 47 to 57, further comprising a solvent.

[0128] 59. The method according to paragraph 58, wherein the solvent is water.

[0129] 60. The method according to any one of paragraphs 47 to 59, wherein the reaction temperature is from about 40 °C to about 100 °C.

[0130] 61. The method according to paragraph 60, wherein the reaction temperature is from about 60 °C to about 70 °C.

[0131] 62. The method according to any one of paragraphs 47 to 61, further comprising a chelating ligand.

[0132] 63. The method according to paragraph 62, wherein the chelating ligand is a bisimine.

[0133] 64. The method according to any one of paragraphs 47 to 63, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

[0134] 65. The method according to any one of paragraphs 47 to 63, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

[0135] 66. The method according to any one of paragraphs 47 to 65, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

[0136] 67. The method according to any one of paragraphs 47 to 66, wherein the reaction mixture is stirred.

[0137] 68. The method according to any one of paragraphs 47 to 67, further comprising quenching the reaction mixture with a quenching agent.

[0138] 69. The method according to paragraph 68, wherein the quenching agent is an amine or water.

[0139] 70. A method for polymerizing one or more cyclic siloxanes, the method comprising:

[0140] Combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula

[0141] wherein n is from 1 to 20 and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, a substituted or unsubstituted aryl group, a hydrogen atom, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amino group, or an alkoxide;

[0142] Treating the reaction mixture with an electrophile T and a nucleophile Z; and

[0143] A product is obtained from a mixture, wherein the product comprises formula (V) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)],

[0144] wherein m > n, Z comprises an amine, an alkoxy group, a trialkylsiloxy group, an acetate, an alkyl ester, a silylazide, a silylamino group or an aminoorganosilicon group, and T comprises an electrophile.

[0145] 71. The method according to paragraph 70, wherein n is from 2 to 10.

[0146] 72. The method according to paragraph 71, wherein n is from 3 to 8.

[0147] 73. The method according to paragraph 72, wherein n is from 4 to 8.

[0148] 74. The method according to any one of paragraphs 70 to 73, wherein the product has a viscosity of from 2,000 cP to about 200 million cP.

[0149] 75. The method according to paragraph 74, wherein the product viscosity is from about 2,500 cP to about 100 million cP.

[0150] 76. The method according to any one of paragraphs 70 to 75, wherein each R is a methyl or ethyl group.

[0151] 77. The method according to any one of paragraphs 70 to 75, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

[0152] 78. The method according to any one of paragraphs 70 to 77, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane and mixtures thereof.

[0153] 79. The method according to paragraph 70, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

[0154] 80. The method according to any one of paragraphs 70 to 79, wherein the Lewis acid catalyst is present in an amount of from 10 ppm to 5,000 ppm based on the weight of the cyclic siloxane.

[0155] 81. The method according to any one of paragraphs 70 to 80 further comprises a solvent.

[0156] 82. The method according to paragraph 81, wherein the solvent is water.

[0157] 83. The method according to any one of paragraphs 70 to 82, wherein the reaction temperature is from about 40 °C to about 100 °C.

[0158] 84. The method according to paragraph 83, wherein the reaction temperature is from about 60 °C to about 70 °C.

[0159] 85. The method according to any one of paragraphs 70 to 84 further comprises a chelating ligand.

[0160] 86. The method according to paragraph 85, wherein the chelating ligand is a bisimine.

[0161] 87. The method according to any one of paragraphs 70 to 86, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

[0162] 88. The method according to any one of paragraphs 70 to 86, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

[0163] 89. The method according to any one of paragraphs 70 to 88, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

[0164] 90. The method according to any one of paragraphs 70 to 89, wherein the reaction mixture is stirred.

[0165] 91. The method according to any one of paragraphs 1 to 90 further comprises the step of adding a crosslinking agent to the polysiloxane product.

[0166] The present invention will be further described with reference to the following non-limiting examples. Those skilled in the art will appreciate that many changes can be made to the described embodiments without departing from the scope of the present invention. Accordingly, the scope of the present invention should not be limited to the embodiments described in this application, but should be defined only by the embodiments described in the language of the claims and the equivalents of those embodiments. Unless otherwise indicated, all percentages are by weight. Examples

[0168] Method for percentage of non-volatile components (NVC)

[0169] Moisture balance was performed using a DSC brand HFT 2000M moisture analyzer (now 4000M). Place the base mat in an aluminum dish and tare to zero. Add 0.5 to 1.0 g of the sample to the base and close the system so that the sample is heated to the set point (130 °C) in a closed chamber. Maintain the temperature until the mass of the sample no longer changes, and calculate the mass change difference (Δm) as NVC.

[0170] An alternative method for determining the residual D4–D10 components is gas chromatography (GC). Use a Shimadzu NexisGC-2030, where the column is a RESTEK 30m x 0.25mm ID with a 0.1 micron film thickness wax column. Prepare the sample by weighing approximately 100 mg of the sample (which is diluted with 10 mL of hexane). Add 1 mL of the solution to a GC vial, and add approximately 200 microliters of hexamethyldisilazane (HMDZ) to the GC vial to quench the reaction. Inject a sample of the quenched reaction mixture into the GC, where the GC curve is at 40 °C, heated at 25 °C / minute, held at 350 °C for 30 minutes, with a total run time of 41 minutes, and a column flow rate of 0.7 mL / minute, a split ratio of 25:10, and compare with a standardized D4–D10 sample to obtain the percentage concentration of the residual cyclic content. The GC method provides a more accurate measurement of NVC.

[0171] All reported molecular weights were calculated using a PDMS standard (311 Da to 305000 Da in toluene). The instrument used was a Shimadzu LC-2050C 3D liquid chromatograph, which has a Shimadzu RID-20A RID detector, with toluene as the eluent, and the GPC column is a Shodex KF-805L 300x8mm pre-column 5um, polystyrene-divinylbenzene, run at 40 °C, 1 mL / min, inject 100 uL. The sample was prepared by placing 100 mg of the sample into a premixed solution of 10 g of toluene and 0.2 g of hexamethyldisilazane, and adding an aliquot to a 1.5 mL HPLC vial. Used to determine M w 、M n and D software is provided by Shimadzu and is called LabSolutions LC / GC, and has a release version of 5.92.

[0172] EXP-15-26-1, Standard D4ROP (Ring-Opening Polymerization), using 250 ppm Bi(TfO)3 catalyst

[0173] Into a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, reflux condenser, and septum, 0.0243 g of Bi(TfO)3 and 99.9857 g of octamethylcyclotetrasiloxane were added. The reaction was stirred and heated to 120 °C using a thermocouple heating plate and a silicone oil bath for 332.9 hours. The M of the final polymer produced by the reaction n was 250941 g / mol, and the M w was 538689 g / mol, and D was 2.15.

[0174] EXP-15-29-1, Standard D5ROP, using 250 ppm Bi(TfO)3 catalyst

[0175] Into a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, reflux condenser, and septum, 0.0273 g of Bi(TfO)3 and 100.88 g of decamethylcyclopentasiloxane were added. The reaction was stirred and heated to 120 °C using a thermocouple heating plate and a silicone oil bath for 238 hours. The M of the final polymer produced by the reaction n was 310433 g / mol, and the M w was 634715 g / mol, and D was 2.04.

[0176] EXP-15-29-2, Standard D6ROP, using 250 ppm Bi(TfO)3 catalyst

[0177] Into a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, reflux condenser, and septum, 0.0262 g of Bi(TfO)3 and 99.9750 g of dodecamethylcyclohexasiloxane were added. The reaction was stirred and heated to 120 °C using a thermocouple heating plate and a silicone oil bath for 238 hours. The M of the final polymer produced by the reaction n was 164987 g / mol, and the M w was 289805 g / mol, and D was 1.76.

[0178] EXP-15-33-1, Equilibrium reaction, 250 ppm Bi(TfO)3 catalyst D5ROP

[0179] Into a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, reflux condenser, and septum, 99.52 g of decamethylcyclopentasiloxane, 0.48 g of hexamethyldisiloxane, and 0.0373 g of Bi(TfO)3 were added. The reaction was stirred and heated to 80 °C using a thermocouple heating plate and a silicone oil bath for 304.6 hours. The M of the final polymer produced by the reaction n was 36733 g / mol, and the M wis 66465 g / mol, and D is 1.81. Hexamethyldisiloxane (HMDS) is used as a capping agent. Depending on the concentration of HMDS, the molecular weight of the final polymer can be controlled. It is an equilibrium polymerization where all the substances are added to the pot and reacted, and depending on the amount of capping in the system, it equilibrates to the possible molecular weight.

[0180] EXP-15-35-1, D5ROP, using 250 ppm Bi(TfO)3 catalyst and 500 ppm H 2 O

[0181] 100.32 g of decamethylcyclopentasiloxane, 50 μL of H2O, and 0.0247 g of Bi(TfO)3 were charged into a 250 mL three-neck round-bottom flask equipped with a magnetic stir bar, a reflux condenser, and a septum. The reaction was stirred and heated to 120 °C for 91.7 h using a thermocouple heating plate and a silicone oil bath. The M of the final polymer produced by the reaction n is 116244 g / mol, M w is 182659 g / mol, and D is 1.57.

[0182] EXP-15-32-1, Standard D5ROP, using 250 ppm Bi(TfO)3 catalyst, reaction completed in oven

[0183] 749.62 g of decamethylcyclopentasiloxane and 0.1870 g of Bi(TfO)3 catalyst were charged into a 1200 mL beaker equipped with an overhead mixer with a stirrer and a thermocouple heating plate. The reaction was heated to 80 °C and mixed using the overhead stirring device. The reaction was covered with aluminum foil to prevent evaporation. The polymerization was allowed to continue until the reaction viscosity exceeded the ability of the overhead mixer to mix the reaction well, which occurred at 29.5 h of the reaction. The remaining reaction was carried out in a 65 °C oven with the beaker completely covered with aluminum foil. The polymerization was carried out for a total of 166.8 h to produce the final polymer, whose M n is 359647 g / mol, M w is 612172 g / mol, and D is 1.70.

[0184] EXP-15-42-1, Disperse EXP-15-32-1 in D5 without quenching

[0185] 339.24 g of decamethylcyclopentasiloxane and 59.85 g of EXP-15-32-1 were charged into a 600 mL beaker equipped with an overhead mixer with a stirrer. The mixture was allowed to mix until the polymer from EXP-15-32-1 was completely dissolved. The polymer dispersion was allowed to stand at ambient conditions for 16 h. The resulting dispersion showed that the M of the EXP-15-32-1 polymer n became 139570 g / mol, M w became 226637 g / mol, and D became 1.62.

[0186] EXP-15-42-2, Disperse EXP-15-32-1 in D5 and quench

[0187] Charge 341.15 g of decamethylcyclopentasiloxane, 40 μL of 15% aqueous sodium hydroxide solution, and 59.88 g of EXP-15-32-1 into a 600 mL beaker equipped with an overhead mixer with a stirrer. Mix the mixture until the polymer from EXP-15-32-1 is completely dissolved. Allow the polymer dispersion to stand for 16 hours under ambient conditions. The resulting dispersion shows that the M n of the EXP-15-32-1 polymer becomes 395223 g / mol, and the M w becomes 753226 g / mol, and D becomes 1.91.

[0188] EXP-9-4-1, Indicating low catalyst loading

[0189] Charge 100 g of D5 and 5 mg of Bi(TfO)3 (50 ppm) into a 150 mL beaker equipped with a magnetic stir bar. Seal the beaker with aluminum foil and control the heating with an in-situ thermocouple to maintain a temperature of 70 °C. After 12 days at 70 °C, the NVC of the solution is 0.45%, indicating a very slow reaction rate. The NVC is determined by the above procedure.

[0190] EXP-9-5-1, Indicating reaction results at low temperature

[0191] Charge 100 g of D5 and 25 mg of Bi(TfO)3 (250 ppm) into a 150 mL beaker equipped with a magnetic stir bar. Seal the beaker with aluminum foil and allow it to stir at room temperature for 12 days. The final NVC of the system is 0.00%, indicating negligible reaction progress. The NVC is determined by the above procedure.

[0192] EXP-8-100-1, Ring-opening polymerization of D5 catalyzed by KOH

[0193] Charge 150 g of D5 and 0.05 g of solid KOH into a 250 mL beaker equipped with a magnetic stir bar. Seal the beaker with aluminum foil and stir and heat to maintain a temperature of 80 °C. After 13 days at 80 °C, the NVC of the solution is 3.79%. The NVC is determined by the above procedure.

[0194] EXP-8-89-1, Trifluoromethanesulfonic acid cocatalyst

[0195] A 600 mL beaker equipped with a magnetic stirrer was charged with 450 g of D5, 65.2 mg of Bi(TfO)3, and 0.1 mL of trifluoromethanesulfonic acid. The beaker was sealed with aluminum foil and heated with a thermocouple to maintain an internal temperature of 75 °C. After two days, the NVC was 32.72%, and the reaction system required mechanical stirring. On the second day, due to excessive viscosity, the fluid could not be stirred, and the reaction was transferred to an oven at 65 °C. Seven days after the start of the reaction, the polymer had an NVC of 98.26%. The NVC was determined by the above procedure.

[0196] EXP-9-10-1, Crosslink EXP-8-81-2 with tetraethyl orthosilicate (TEOS)

[0197] 50 g of the EXP-8-81-2 polymer was charged into a 200 mL high-speed mixing cup. The polymer was premixed at 2300 rpm for 30 seconds, and then the high-speed mixing cup containing the glue was charged with 0.1 g of TEOS and mixed at high speed at 2300 rpm for 1.5 minutes at 30-second intervals. The resulting viscous flowing liquid solidified as water and ethanol evaporated to form an elastic rubber.

[0198] This example is very similar to the reversible molecular weight modification pointed out herein, but instead of using a monofunctional alcohol, an alkoxysilane was used to tie together a variety of polymers to form a transparent room-temperature curing, such as crosslinked rubber.

[0199] EXP-15-36-5, 15-32-1 glue, using methyltrimethoxysilane, crosslinking modification

[0200] 26.44 g of the 15-32-1 polymer and 1.12 g of methyltrimethoxysilane were charged into an 8-ounce high-speed mixing cup. The mixture was mixed at high speed at 2300 RPM at 30-second intervals until the alcohol was consumed in the reaction. The resulting polymer showed that the M of the EXP-15-32-1 polymer n became 13077 g / mol, M w became 86363 g / mol, and D became 6.60. Approximately 2 g of the resulting methyltrimethoxysilane-modified polymer was exposed to environmental conditions and air for 16 hours. The polymer had crosslinked into a transparent elastomer and was subsequently insoluble in toluene.

[0201] EXP-15-36-8, 15-32-1 glue, using 4% methanol, reversible MW modification

[0202] 25.33 g of the 15-32-1 polymer and 1.05 g of methanol were charged into an 8-ounce high-speed mixing cup. The mixture was mixed at high speed at 2300 RPM at 30-second intervals until the alcohol was consumed in the reaction. The resulting polymer showed that the M of the EXP-15-32-1 polymer n became 38856 g / mol, M wThe molecular weight of the resulting methanol-modified polymer was changed to 72582 g / mol, and D was changed to 1.87. Approximately 2 g of the resulting methanol-modified polymer was exposed to ambient conditions and air for 16 hours. The polymer was analyzed again by GPC and it was shown that the polymer had recovered to its initial high molecular weight, M n becomes 335430 g / mol, M w becomes 670115 g / mol, and D becomes 2.00.

[0203] The above examples demonstrate not only the ability of the polymer product to react directly with alcohol, but also that it rapidly results in a decrease in the molecular weight and viscosity of the polymer. Interestingly, if the resulting alcohol functionalized polymer (which is a free-flowing liquid) is exposed to the atmosphere for several hours, it recovers to a high molecular weight. Without being limited by theory, the alcohol may be inserted into the backbone of the organosilicon, and the Si-OC bonds are hydrolysis sensitive, and at sufficient humidity, alcohol loss ensues and recovery to the original polymer product.

[0204] EXP-9-7-2, Disperse the polymer from EXP8-81-2 in D5 using a quenching agent.

[0205] KOH was utilized because a better clarity mixture was achieved compared to NaOH.

[0206] A 600 mL beaker equipped with a mechanical overhead stirrer and a 4-blade propeller stirrer was charged with 340 g of D5, 60 g of the polymer produced in EXP-8-81-2, and 40 μL of 50% aqueous KOH. After 24 hours, the product produced by this experiment had a viscosity of 2610 cP and an NVC of 12.35%.

[0207] M n It is calculated by fitting the GPC raw data to the PDMS standard calibration curve.

[0208] M w It is calculated by fitting the GPC raw data into the DM standard calibration curve.

[0209] D is the M obtained using the GPC data w and M n , through PDI = M w / M n Calculate the polydispersity index.

[0210] EXP 8-81-2 Charge 16.32 kg of D5 and 2.5 g of Bi(TfO)3 (150 ppm) into a 5-gallon stainless steel container equipped with an overhead stirrer and a thermocouple heating plate. After 9 days, the NVC is 30.08%. Then transfer the reaction mixture to a polyethylene 5-gallon bucket and seal it with a lid. Then place the bucket in a 160°F hot room. After 5 days at high temperature, the NVC is 82.67%, after 6 days the NVC is 86.49%, after 8 days the NVC is 96.64%, and after 10 days the NVC is 97.5%. Use GC (the method described above) to analyze the reaction product to achieve a D4 wt% of 4.81%, a D5 wt% of 4.36%, and a D6 wt% of 1.19%.

[0211] EXP9-15-1

[0212] Charge 139.25 kg of D5 into an open 55-gallon steel drum equipped with an electric heating blanket and a drum mixer. Heat D5 with stirring, where the blanket set temperature is 225°F. After several hours, add 34.81 g of Bi(TfO)3 to the reaction. The measured reaction temperature is 125°F. Stop heating overnight, but continue to stir the reaction mixture. The next morning, the temperature of the reaction mixture is 133°F, and the reaction mixture has an NVC of 17.04%. Over the next six hours, the NVC is 41.91%, and the reaction mixture has a viscosity of 185,500 cP (measured on a Brookfield DVNext cone plate viscometer using cone CP-52 at 3 RPM and 25°C). After that, seal the reaction drum and place it in a 160°F hot room. After 3 days of heating, the NVC is 98.10%, and after 4 days of heating, the NVC is 98.46%. Use GC analysis with the method discussed previously to yield a D4 wt% of 4.99%, a D5 wt% of 3.68%, and a D6 wt% of 1.24%.

[0213] EXP 8-92-1

[0214] Charge 72 g of the EXP 8-81-2 product and 328 g of isododecane into a 600 mL glass beaker equipped with an overhead stirrer. Mix the mixture until homogeneous. The final viscosity is 60 cP, and the final NVC is 14.04%. Use GC analysis with the method described previously to yield a D4 wt% of 0.47%, a D5 wt% of 0.02%, and a D6 wt% of 0.24%. Measure the final viscosity via DV2T and find it to be 60 cP.

[0215] EXP 8-92-2

[0216] Charge a 600 mL glass beaker equipped with an overhead stirrer with 72 g of EXP 8-81-2 product, 328 g of isododecane, and 0.2 g of hexamethyldisilazane. Mix the mixture until homogeneous. The final viscosity is 1750 cP, and the final NVC is 14.37%. GC analysis was performed using the method described previously, yielding 0.82% D4 wt%, 0.03% D5 wt%, and 0.22% D6 wt%. The final viscosity of 1750 cP was found via DV2T.

[0217] EXP 9-16-2

[0218] Charge a 600 mL glass beaker equipped with an overhead stirrer with 340 g of D5, 60 g of EXP 9-15-1 product, and 40 μL of 15% aqueous NaOH solution. Mix the mixture until homogeneous, and a fluid with a viscosity of 9750 cP and an NVC of 11.84% is produced. GC analysis yields 0.79% D4 wt% and 2.0% D6 wt%. Allow the mixture to age for 14 days. Monitor the changes in NVC and viscosity of the reaction product. Test NVC using the moisture balance and measure the viscosity at 25 °C at 6 rpm using a Brookfield DV2T viscometer with spindle LV-3, the value being 9750 cP. During the test, keep the sample sealed in a 50 °C oven to accelerate aging.

[0219] Day Viscosity (cP) NVC % 1 9750 11.84 6 10300 12.01 8 10620 12.93 14 10240 12.15

[0224] EXP-15-37-3, 15-32-1 glue, using 1% ethanol

[0225] Charge an 8-ounce high-speed mixer cup with 30.28 g of 15-32-1 polymer and 0.29 g of absolute ethanol. Mix the mixture at 2300 RPM at 30-second intervals in a high-speed mixer until the alcohol is consumed in the reaction. The resulting polymer shows that the M n of the EXP-15-32-1 polymer becomes 43511 g / mol, the M w becomes 80600 g / mol, and D becomes 1.85. Mix high-speed mixer samples using an 8-ounce container in a Flactec DAC1200-300 high-speed mixer at 2300 rpm at 30-second intervals.

[0226] EXP-15-40-1, 15-32-1 glue, using 1000 ppm ethanol

[0227] Charge an 8-ounce high-speed mixing cup with 30.91 g of 15-32-1 polymer and 0.03 g of absolute ethanol. Mix the mixture at 2300 RPM at 30-second intervals until the alcohol is consumed in the reaction. The resulting polymer shows that the M of EXP-15-32-1 polymer n becomes 95932 g / mol, and the M w becomes 166252 g / mol, and the D becomes 1.73. Mix the high-speed mixer samples using an 8-ounce container at 2300 rpm at 30-second intervals using a Flactec DAC 1200-300 high-speed mixer.

[0228] EXP-15-44-1, 15-32-1 glue, using 500 ppm ethanol

[0229] Charge an 8-ounce high-speed mixing cup with 16.64 g of 15-32-1 polymer and 10.5 μL of absolute ethanol. Mix the mixture at 2300 RPM at 30-second intervals until the alcohol is consumed in the reaction. The resulting polymer shows that the M of EXP-15-32-1 polymer n becomes 260856 g / mol, and the M w becomes 487426 g / mol, and the D becomes 1.87.

[0230] EXP-15-36-9, 15-32-1 glue, using 4% 1-butanol

[0231] Charge an 8-ounce high-speed mixing cup with 26.72 g of 15-32-1 polymer and 1.12 g of 1-butanol. Mix the mixture at 2300 RPM at 30-second intervals until the alcohol is consumed in the reaction. The resulting polymer shows that the M of EXP-15-32-1 polymer n becomes 15745 g / mol, and the M w becomes 27998 g / mol, and the D becomes 1.78.

[0232] Although the present invention has been described with reference to the preferred embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. All references cited throughout the specification, including those in the background, are hereby incorporated by reference in their entirety. Those skilled in the art will recognize, or be able to determine using only routine experimentation, many equivalents to the specific embodiments of the invention specifically described herein. Such equivalents are intended to be encompassed by the scope of the claims.

Claims

1. A method for polymerizing one or more cyclic siloxanes, the method comprising: combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula where n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, substituted or unsubstituted aryl group, hydrogen atom, substituted or unsubstituted alkenyl group, substituted or unsubstituted amino group or alkoxide; and A product is obtained from the mixture, wherein the product comprises formula (II) [(HO)R2SiO 1 / 2 2(R2SiO2 / 2) m , where m > n.

2. The method according to claim 1, wherein n is from 2 to 10.

3. The method according to claim 2, wherein n is from 3 to 8.

4. The method according to claim 3, wherein n is from 4 to 8.

5. The method according to claim 1, wherein the product has a viscosity of from 2,000 cP to about 200 million cP.

6. The method according to claim 5, wherein the product has a viscosity of from about 2500 cP to about 100 million cP.

7. The method according to claim 1, wherein each R is a methyl or ethyl group.

8. The method according to claim 1, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

9. The method according to claim 1, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane and mixtures thereof.

10. The method according to claim 9, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

11. The method according to claim 1, wherein the Lewis acid catalyst is present in an amount of from 10 ppm to 5000 ppm based on the weight of the cyclic siloxane.

12. The method according to claim 1, further comprising a solvent.

13. The method according to claim 12, wherein the solvent is water.

14. The method according to claim 1, wherein the reaction temperature is from about 40 °C to about 100 °C.

15. The method according to claim 14, wherein the reaction temperature is from about 60 °C to about 70 °C.

16. The method according to claim 1, further comprising a chelating ligand.

17. The method according to claim 16, wherein the chelating ligand is a bisimine.

18. The method according to claim 1, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

19. The method according to claim 1, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

20. The method according to claim 1, wherein the chelating ligand is present in an amount of from 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

21. The method according to claim 1, wherein the reaction mixture is stirred.

22. The method according to claim 1, further comprising quenching the reaction mixture with a quenching agent.

23. The method according to claim 22, wherein the quenching agent is an amine or water.

24. A method for polymerizing one or more cyclic siloxanes, the method comprising: Combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of from about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula where n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, substituted or unsubstituted aryl group, hydrogen atom, substituted or unsubstituted alkenyl group, substituted or unsubstituted amino group or alkoxide; Treating the reaction mixture with a nucleophile Z; and A product is obtained from a mixture, wherein the product comprises formula (III) [(HO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)], where m > n and Z comprises an amine, an alkoxy group, a trialkylsiloxy group, an acetate, an alkyl ester, a silylazanyl, a silylcarbamoyl group or an aminoorganosilicon group.

25. The method according to claim 24, wherein n is from 2 to 10.

26. The method according to claim 25, wherein n is from 3 to 8.

27. The method according to claim 26, wherein n is from 4 to 8.

28. The method according to any one of claims 24 to 27, wherein the product has a viscosity of from 2,000 cP to about 200 million cP.

29. The method according to claim 28, wherein the product viscosity is from about 2,500 cP to about 100 million cP.

30. The method according to claim 24, wherein each R is a methyl or ethyl group.

31. The method according to claim 24, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

32. The method according to claim 24, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane, and mixtures thereof.

33. The method according to claim 32, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

34. The method according to claim 24, wherein the Lewis acid catalyst is present in an amount of from 10 ppm to 5,000 ppm based on the weight of the cyclic siloxane.

35. The method according to claim 24, further comprising a solvent.

36. The method according to claim 35, wherein the solvent is water.

37. The method according to claim 24, wherein the reaction temperature is from about 40 °C to about 100 °C.

38. The method according to claim 37, wherein the reaction temperature is from about 60 °C to about 70 °C.

39. The method according to claim 24, further comprising a chelating ligand.

40. The method according to claim 39, wherein the chelating ligand is a bisimine.

41. The method according to claim 24, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

42. The method according to claim 24, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

43. The method according to claim 24, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

44. The method according to claim 24, wherein the reaction mixture is stirred.

45. The method according to claim 24, further comprising quenching the reaction mixture with a quenching agent.

46. The method according to claim 45, wherein the quenching agent is an amine.

47. A method for polymerizing one or more cyclic siloxanes, the method comprising: combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane has the formula where n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, substituted or unsubstituted aryl group, hydrogen atom, substituted or unsubstituted alkenyl group, substituted or unsubstituted amino group or alkoxide; treating the reaction mixture with an electrophile T; and Obtaining a product from a mixture, wherein the product comprises formula (IV) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(OH)], where m > n and T comprises an electrophile.

48. The method according to claim 47, wherein n is from 2 to 10.

49. The method according to claim 48, wherein n is from 3 to 8.

50. The method according to claim 49, wherein n is from 4 to 8.

51. The method according to claim 47, wherein the product has a viscosity of 2,000 cP to about 200 million cP.

52. The method according to claim 47, wherein the product viscosity is from about 2500 cP to about 100 million cP.

53. The method according to claim 47, wherein each R is a methyl or ethyl group.

54. The method according to claim 47, wherein each R is independently one of a methyl group, an ethyl group, or a phenyl group.

55. The method according to claim 47, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane, and mixtures thereof.

56. The method according to claim 55, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

57. The method according to claim 47, wherein the Lewis acid catalyst is present in an amount of 10 ppm to 5000 ppm based on the weight of the cyclic siloxane.

58. The method according to claim 47, further comprising a solvent.

59. The method according to claim 58, wherein the solvent is water.

60. The method according to claim 47, wherein the reaction temperature is from about 40 °C to about 100 °C.

61. The method according to claim 60, wherein the reaction temperature is from about 60 °C to about 70 °C.

62. The method according to claim 47, further comprising a chelating ligand.

63. The method according to claim 62, wherein the chelating ligand is a bisimine.

64. The method according to claim 47, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

65. The method according to claim 47, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

66. The method according to claim 47, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

67. The method according to claim 47, wherein the reaction mixture is stirred.

68. The method according to claim 47, further comprising quenching the reaction mixture with a quenching agent.

69. The method according to claim 68, wherein the quenching agent is an amine or water.

70. A method for polymerizing one or more cyclic siloxanes, the method comprising: combining one or more cyclic siloxanes with a Lewis acid catalyst at a temperature of about 20 °C to about 400 °C to form a reaction mixture, wherein the cyclic siloxane comprises the formula where n is from 1 to 20, and each R is independently a substituted or unsubstituted C1 to C 20 alkyl group, substituted or unsubstituted aryl group, hydrogen atom, substituted or unsubstituted alkenyl group, substituted or unsubstituted amino group or alkoxide; treating the reaction mixture with an electrophile T and a nucleophile Z; and Obtaining a product from a mixture, wherein the product comprises formula (V) [(TO)R2SiO 1 / 2 (R2SiO2 / 2) m [SiO 1 / 2 R2(Z)] where m > n, Z includes an amine, an alkoxy group, a trialkylsiloxy group, an acetate, an alkyl ester, a silylazide, a silylamino group or an aminoorganosilicon group, and T includes an electrophile.

71. The method according to claim 70, wherein n is from 2 to 10.

72. The method according to claim 71, wherein n is from 3 to 8.

73. The method according to claim 72, wherein n is from 4 to 8.

74. The method according to claim 70, wherein the product has a viscosity of 2,000 cP to about 200 million cP.

75. The method according to claim 74, wherein the product viscosity is about 2500 cP to about 100 million cP.

76. The method according to claim 70, wherein each R is a methyl or ethyl group.

77. The method according to claim 70, wherein each R is independently one of a methyl group, an ethyl group or a phenyl group.

78. The method according to claim 70, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, scandium(III) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, dicyclohexylboron trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, cerium(IV) trifluoromethanesulfonate, nonafluorobutane-1-sulfonic acid, trifluoromethanesulfonic acid, phosphazene chloride, zinc(II) trifluoromethanesulfonate, samarium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, boron trihalide, organoborane and mixtures thereof.

79. The method according to claim 70, wherein the Lewis acid catalyst is bismuth(III) trifluoromethanesulfonate.

80. The method according to claim 70, wherein the Lewis acid catalyst is present in an amount of 10 ppm to 5000 ppm based on the weight of the cyclic siloxane.

81. The method according to claim 70, further comprising a solvent.

82. The method according to claim 81, wherein the solvent is water.

83. The method according to claim 70, wherein the reaction temperature is from about 40 °C to about 100 °C.

84. The method according to claim 83, wherein the reaction temperature is from about 60 °C to about 70 °C.

85. The method according to claim 70, further comprising a chelating ligand.

86. The method according to claim 85, wherein the chelating ligand is a bisimine.

87. The method according to claim 70, wherein the chelating ligand is combined with the Lewis acid catalyst before combining the Lewis acid with the cyclic siloxane.

88. The method according to claim 70, wherein the chelating ligand is combined with the reaction mixture after combining the Lewis acid catalyst with the cyclic siloxane.

89. The method according to claim 70, wherein the chelating ligand is present in an amount of 10 ppm to 1000 ppm based on the weight of the cyclic siloxane.

80. The method according to claim 70, wherein the reaction mixture is stirred.

91. The method according to any one of claims 1 to 90, further comprising the step of adding a crosslinking agent to the polysiloxane product (II), (III), (IV) or (V).

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